Flame retardant compositions

ABSTRACT

Novel flame retardant compositions of matter comprise a mixture of a polymeric material and a polyhalo-substituted polyhydropolycyclicdicarboxylic acid or anhydride thereof. These novel compositions of matter may be exemplified by a mixture of polypropylene and 5,6,7,8,9,9-hexachloro-6,7-dibromomethylene1,2,3,4,4a,5,8,8a-methano-2,3 -naphthalenedicarboxylic anhydride.

l U 5""18 e E3 5?? RKMMR 145% 3 9 5556 9 815 33 1,; WV! I; United State1111 3,856,888 Schmerling Dec. 24, 1974 FLAME RETARDANT COMPOSITIONS3,050,567 8/1962 Schmerling 2611/6148 I L S h l. In 3,152,172 lO/1964Roberts et a1. .1 260/468 [75] nvemorc Rlverslde, 3,265,745 8/1966Seyferth et al..... 260/648 73 AssigneeZ Universal 0 Products Company,3,346,597 10/1967 De Aceus 2611/3463 Des Plaines I. 3,418,384 12/1968Stapp 2610/6413 [22] Filed: 1974 Primary ExaminerV. P. Hoke [21] Appl.No.: 464,709 Attorney, Agent; or Firm-James R. Hoatson, Jr,;

Related Us. Application Data Raymond 1-1. Nelson; W1ll1am H. Page, II[63] Continuation-impart of Ser. No. 302,988, Nov. 1

[57 ABSTRACT [52] US. Cl. 260/881, 106/15 FP, 260/45.8 A, Novel flameretardant compositions of matter com- 260/45.85 T .prise a mixture of apolymeric material and a polyha- Int.

Cosd C081 g 5 /58 lo-substituted polyhydropolycyclicdicarboxylic acid or[58] eld O Searc -H. 2 /4 45.85 514 G, anhydride thereof. These novelcompositions of mat 260/ 6. 34643, 648 648 881 ter may be exemplifieclbya mixture of polypropylene 106/15 FF and5,6,7,8,9,9-he7k.achloro-6,7-dibromomethylene-1,2,3,4,4a,5,8,8a-methano-2,3- [56] References Citednaphthalenedicarboxylic anhydride. UNITED STATES PATENTS 8 Cl N D3,017,431 l/l962 Schmerling 260/514 9 rawmgs CROSS-REFERENCE TO RELATEDAPPLICATIONS 5,6,7,8,9,9-hexachloro-6,7-dibromomethylene- 1,2,3 ,4,4a,5,8,8a-octahydro- ,8-methano-2,3-

" i naphtlialenedicarboxylic 7 This application is acontinuation-in-part of my copending application Ser. No. 302,988 filedNov. 1, 1972, all teachings of which are expressly incorporated hereinby reference.

This invention relates to novel compositions of matter comprising amixture of polymeric material which is flammable in nature and apolyhalosubstituted polyhydropolycyclicdicarboxylic acid or anhydridethereof. More specifically, the invention relates to these novelcompositions of matter in which the aforesaid polyhalo-substitutedpolyhydropolycyclicdicarboxylic acid or anhydride thereof ischaracterized by possessing a dihalo-substituted methylene radical in a3 membered ring.

It has now been discovered thatnovcl flame retardant compositions ofmatter may be admixing a polyhalo-substitutedp0lyhydropolycyclicdicarboxylic acid or anhydride thereof containing adihalo-substituted methylene radical in a 3 membered ring with apolymeric material either synthetic or naturally occurring to nature toimpart desired flame retardancy or fire resistant characteristics to thefinished material. The aforementioned polyhalo-substitutedpolyhydropolycyclicdicarboxylic acids or anhydrides thereof are usefulas additives to plastics, polymers, copolymers, terpolymers, resins,polycondensates, elastomers, rubbers, textiles and fibers, wood andpaper, both naturally occurring and synthetic in nature, coatings,paints, varnishes, leather foams, cellulose acetate butyrate, ethylcellulose, cellulose propionate, polyolefins'such as polyethylene andpolyethylene copolymers, synthetic polyetehylene paper, polypropyleneand polypropylene copolymers, polystyrenes, polystyrene copolymers,polyvinyl acetate or alcohol and copolymers, polyvinyl chloride andcopolymers, polyvinylidene chloride and copolymers, polyesters,polyurethane, polyphenyl ethers, styrenated polyphenyl ethers,polycarbonates, polyamides, polyoxymethylenes, polyalkylene oxides suchas polyethylene oxide, polyacrylates, polymethacrylates and theircopolymers with styrene, butadiene, acrylonitrile, etc., epoxy resins,butadiene-styrene formulations (commonly known as ABS), polybutylene andacrylic ester-modified-styreneacrylonitrile (ASA), etc., whereby thedesired physical characteristics of flameproofing or fire retardancywill be imparted to the aforementioned materials. By utilizing thecompounds of the present invention, a catalytic and/or synergisticaction in which the fire retardance or flameproofing will be greatlyenhanced will occur. This particular physical characteristic willpossess special advantages when preparing plastics, polymers, resins,various rubbers, textiles, etc., which will be utilized in places whichmay be subjected to excessive heat or to the action of a possible flame,such places including architectural panels for construction work, wallplugs for electrical connections, soundproofing material in walls,ceilings, etc., under hood automotive use, heater ducts, cable and wirecoatings, TV-cabinets, appliance housing, car or airplane interiorcomponents, automotive vents, etc., boat interiors or exteriors,cushions for various vehicle seats such as airplane seats, automobileacrylonitrileseats, bus seats, etc. In addition, the compound whenutilized as a constituent of paint, lacquer, varnishes, or protectivecoatings, films, etc., will also impart a flame resistance to thesecompounds and, therefore, render them commercially attractive asarticles of commerce. Also, besides imparting the desirable physicalcharacteristics of flame retardancy to the various articles ofmanufacture, the additives will render certain polymeric compositions ofmatter more stable to color changes and, therefore, will be importantcomponents of these compounds whenever it is desirable thatdiscoloration of the finished product is to be avoided or will tend torender such articles unusable.

It is therefore an object of this invention to provide novelcompositions of matter which possess desirable physical properties.

Another object of this invention is to provide novel compositions ofmatter which possess the desirable physical characteristics of flameretardancy or fire resistance, said compositions of matter comprising amixture of a polymeric material and a polyhalo-substitutedpolyhydropolycyclicdicarboxylic acid or anhydride thereof. I

In one aspect an embodiment of this invention is found in a flameretardant composition of matter comprising a polymeric material and apolyhalo-substituted polyhydropolycyclidicarboxylic acid or anhydridethereof having the formula:

- ter comprising a mixture of a polymeric material and apolyhalo-substituted polyhydropolicyclicdicarboxylic acid of anhydridethereof in which said acid or anhydride is characterized by containing adihalo-,

substituted methylene in a 3 membered ring, said compositions of matterpossessing certain characteristics such as the ability to retard flamesor be fire resistant. The polyhalo-substitutedpolyhydropolycyclicdicarboxylic acid or anhydride which comprises onecomponent of the novel composition of matter may be prepared bycondensing a polyhalo-substituted polyhydropolycyclicdicarboxylic acidor anhydride thereof with a phenyl(trihalomethyl)mercury compound atreaction conditions which are hereinafter set forth in greater detail.Any suitable polyhalosubstituted polyhydropolycyclicdicarboxylic acid oranhydride thereof may be used in the preparation of the desiredcompound, said polyhalo-substituted polyhydropolycyclicdicarboxylic acidor anhydride thereof being illustrated by the following generalformulae:

in which X is selected from the group consisting of hydrogen and halogenradicals (particularly chlorine and- /or bromine), at least two of theXs being halogen and n ranges from O to 1. Representative examples ofthese polyhalo-substituted polyhydropolycyclicdicarboxylic acids oranhydrides thereof which may be utilized includel,4,5,6,7,7-hexachlorobicyclo[2.2.l]:5-heptene- 2,3-dicarboxylic acid oranhydride thereof which may be prepared by condensing maleic acid ormaleic anhydride with hexachlorocyclopentadiene, l,4,5,6-tetrachlorobicyclo[2.2.l ]-5-heptene-2,3-dicarboxylic acid or anhydridewhich may be prepared by condensing maleic acid or maleic anhydride with1,2,3,4- tetrachloro-l,3-cyclopentadiene. Another example of the acid oranhydride which may be used comprises 5,-6,7,8,9,9-hexachloro-l,2,3,4,4a,-5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid or anhydride thereof which isprepared by condensing a conjugated aliphatic diene such as1,3-butadiene with maleic acid or maleic anhydride and thereafterfurther condensing the resultant cyclohexene acid or anhydride thereofwhich is l,2,3,-tetrahydrophthalic acid or anhydride thereof withhexachlorocyclopentadiene to form the desired product. It is to beunderstood that the corresponding bromo-substituted compounds may beprepared in like manner by utilizing hexabromocyclopentadiene in placeof the hexachlorocyclopentadiene. Likewise it is to be understood thatother starting materials may also be utilized to form suitable acids oranhydrides, illustrative examples of these starting materials includingother acids such as fumaric acid, itaconic acid, citraconic acid,glutaconic acid, etc.; conjugated aliphatic dienes including 2-methyl-l,3- butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4- hexadiene,2,3-dimethyl-l,3-butadiene, 1,3-

heptadiene, 2,4-heptadiene, conjugated octadienes, nonadienes, etc.; orother halo-substituted cycloalkadienes includingl,2-dichlorocyclopentadiene, 1,2,3-trichlorocyclopentadiene,1,2,3,4-tetrachlorocyclopentadiene, l,2,3,4,5-pentachlorocyclopentadieneand similar compounds in which all or part of the chlorine is replacedby other halogen atoms, particularly bromine.

The aforementioned polyhalo-substituted polyhydropolycyclicdicarboxylicacids or anhydrides thereof are condensed with aphenyl(trihalomethyl)mercury compound, the compound being characterizedby containing at least one bromine atom, in a thermal reaction in thepresence of a solvent of the type hereinafter set forth in greaterdetail. Examples of phenyl- (trihalomethyl)mercury compounds which maybe used will include phenyl(tribromomethyl)mercury,phenyl(dibromochloromethyl)mercury, phenyl(dichlorobromomethyl)mercury,etc.

The condensation is effected at elevated temperatures and preferably atthe reflux temperature of the solvent which is utilized. Thesetemperatures will range from about 30 C. up to about 150 C. Examples ofsubstantially inert organic solvents which may be used will include theparaffinic solvents such as n-pentane, nhexane, n-heptane, cyclopentane,cyclohexane, methylcyclopentane, cycloheptane, etc.; aromatic solventssuch as benzene, toluene, the isomeric xylenes, ethylbenzene, etc. Whilethe condensation is usually effected at atmospheric pressure, it is alsocontemplated within the scope of this invention that superatmosphericpressures ranging from 2 to atmospheres or more may be utilized. Ifsuperatmospheric pressures are to be employed, the aforesaid pressure isafforded by the introduction of a substantially inert gas such asnitrogen into the reaction zone, the amount of pressure utilized beingthat which is sufficient to maintain a major portion of the reactants inthe liquid phase.

The process in which the acid or anhydride which comprises one componentof the novel composition of matter of the present invention may beeffected in any suitable manner and may comprise either a batch orcontinuous type operation. For example, when a batch type operation isused, a quantity of the particular acid or anhydride andphenyl(trihalomethyl)-mercury compound is placed in an appropriateapparatus along with the particular solvent. The apparatus, which maycomprise a condensation flask, or if superatmospheric pressures are tobe employed, an autoclave of the rotating or mixing type, is providedwith heating means whereby the vessel is heated to the particulardesired operating temperature which is, as hereinbefore set forth, whenusing atmospheric pressure conditions, the reflux temperatureof thesolvent. The reaction is allowed to proceed for a predeterminedresidence time which may range from about 0.5 hours (or, occasionally,less) up to about 10 hours (or more), in duration. At the end of thistime, the apparatus and contents thereof are allowed to cool to roomtemperature, the excess pressure, if any, is discharged and the reactionproduct is recovered. The product is separated from the solvent byconventional means such as distillation, by precipitation, by dilutingthe solvent with a non-solvent, evaporation, suction, filtration,extraction, etc. and subjected to conventional means of purificationwhereby the desired polyhalo-substituted polyhydropolycyclicdicarboxylicacid or anhydride thereof characterized by containing adihalo-substituted methylene substituent on one of the rings isrecovered.

-It is also contemplated within the scope of this invention that thedesired polyhalo-substituted polyhydropolycyclicdicarboxylic acid oranhydride containing the particular configuration which characterizesthe novel compounds of this invention may be prepared by utilizing acontinuous manner of operation. When such a type of operation is used,the starting materials comprising the particular acid or anhydride andthe phenyl(trihalomethyl)mercury compound are continuously charged to areactor which is maintained at the proper operating conditions oftemperature and pressure. The solvent which is utilized in the reactionmay be also charged to the reactor through a separate line or may beadmixed with one or both of the starting materials prior to entry intosaid reactor and-the mixture charged thereto in a single stream. Uponcompletion of the desired time, the reactor effluent is continuouslywithdrawn and the reaction product is isolated by conventional means ofthe type hereinbefore set forth, the unreacted starting material whichmay be present in the effluent being recycled to form a portion of thefeed in which Y is chlorine or bromine, X is hydrogen or halogen, atleast two Xs being halogen and n is zero or 1. Some representativeillustrative examples of these compounds will include 5,8-dichloro-6,7-dibromomethylene-l ,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid; 5,8-dichloro-6,7-dibromomethylene-l,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylicanhydride, 5,6,7,8-tetrachloro-6,7-dibromomethylene- 1,2,3,4,4a, 5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylic acid,5,6,7,8-tetrachloro-6,7-dibromomethylene-1,2,3,4,4a,5,8,8a-octahydro-5,8-methane-2,3-naphthalenedicarboxylic anhydride, 5,6,-7,8,9,9-hexachloro-6,7-dibromomethylene- 1,2,3,4,4a,5,8,8a-octahydro5,8-methano-2,3- naphthalenedicarboxylic acid;5,6,7,8,9,9-hexachloro- 6,7-dibromomethylene-l,2,3,4,4a,-5,8,8a-octahydro- 5,8-methan-2,3-naphthalenedicarboxylicanhydride,5,6-dibromo-6,7-dibromomethylene-1,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylicacid; 5,6-dibromo-6,7-dibromomethylene-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicanhydride, 5,6,7,8-tetr-abromo-6,7-dibromomethylene-1,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylicacid; 5,6,7,8-tetrabromo-6,7-dibromomethylene- 1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicanhydride, 5,6,7,8,9,9-hexabromo-6,7-dibromomethylene-l,2,3,4,4a,-5,8,8aoctahydro-S,8-methano-2,3-napthalenedicarboxylicacid, S,6,7,8,9,9-hexabromo-6,7-dibromomethylene- 1,2,3 ,4,4a,5,8,8a-octahydro- ,8-methano-2,3- naphthalenedicarboxylic anhydride;5,6,7,8-tetrachloro-6,7-dichloromethylene-1,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-napl1thalenedicarboxylicacid, 5,6,7,8-tetrachloro-6,7-dichloromethylene- 1,2,3,4;4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicanhydride; 5,6,7,8,9,9- hexachl0r0-6,7-dichloromethylene-l ,2,3 ,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylic acid,5,6,7,8,9,9-hexachloro-6,7-dichloromethylene- 1,2,3,4,4a,-5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylic anhydride, l,4-dichloro-5,6- dibromomethylenebicyclo[2.2.l ]heptane-2,3- dicarboxylicanhydride, 1,4-dichloro-5 ,6- dibromomethylenebicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 1,4,5,6-tetrachloro-5,6-dibromomethylenebicyclo[2.2.1]heptane-2,3- dicarboxylic acid,l,4,5,6-tetrachl0ro-5,6- dibromomethylenebicyclo[2.2.1]heptane- 2,3-

dicarboxylic 6 dicarboxylic acid, l,4,5,6-tetrachloro-5.6-dibromomethylenebicyclo[2.2.1]heptane- 2,3dicarboxylic anhydride, l,4,5,6,7,7-hexachloro-5,6- dibromomethylene-bicyclo[2.2.1]heptane2,3-dicarboxylic acid, 1,4,5 ,6,7,7-hexachloro-5 ,6-dibromomethylenebicyclo[2.2.1]heptane-2,3- dicarboxylic anhydride,1,4,5,6,7,7-hexachloro-5,6- dichloromethylenebicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5,6-dichloromethylenebicyclo[2.2.1]heptane-2,3- dicarboxylic anhydride,1,4,5,6-tetrabromo-5,6- dibromomethylenebicyclo[2.2.l ]-heptane-2,3-dicarboxylic acid, 1,4,5,6-tetrabromo-5,6- dibromomethylenebicyclo[2.2.l]heptane-2,3- dicarboxylic anhydride, 1,4,5,6,7,7-hexabromo-5,6-dibromomethylenebicyclo[2.2.1]heptane-2,3-

acid; 1,4,5,6,7,7-hexabromo-5,6- dibromomethylenebicyclo[2.2.l]heptane-2,3- dicarboxylic anhydride, 1,4,5 ,6-tetrabromo-5 ,6-dichloromethylenebicyclo[2.2.1]heptane-2,3- dicarboxylic acid, 1,4,5,6-tetrabromo-5 ,6- dichloromethylenebicyclo[2.2.1 ]-heptane'-2,3-dicarboxylic anhydride; 1,4,5,6,7,7-hexabromo-5,6-dichloromethylenebicyclo[2.2.l ]heptane-2,3- dicarboxylic acid, 1,4,5,6,7,7-hexabromo-5 ,6- dichloromethylenebicyclo[2.2. l ]heptane-2,3-dicarboxylic anhydride, etc. It is to be understood that theaforementioned compounds are only representative of the class ofcompounds of the present invention and that said invention is notnecessarily limited thereto.

The aforementioned polyhalo-substituted polyhydropolycyclicdicarboxylicacid or anhydride characterized by containing a dihalo-substitutedmethylene in a 3 membered ring may be composited with polymericcompounds of the type hereinbefore set forth to form novel flameretardant compositions of matter, said polymeric compounds comprisingplastics, resins, polymers, copolymers, textiles, etc. For example, thepolyhalo-substituted polyhydropolycyclicdicarboxylic acids or anhydridesmay be used as additivesto polyolefins such as polypropylene whereby thefinal product will possess advantageous physical properties such as anincreased stability against deterioration, weathering, and aging whichhasbeen induced by chemical, physical or biological agents or radiation.In addition, the polyolefins will also possess a high ignition point aswell as a high degree of flame retardancy. The acids or anhydrides maybe added to the polyolefins such as polyethylene, polypropylene in arange of from about 5 to about 50 percent by weight of the polymericmaterial to be treated. Thereafter, it will be found that the. oxygenindex of the polyolefins will have been increased, while the burningrate will be decreased. Ex-

amples of other polymeric products will be treated with the acids oranhydrides of the type hereinbefore set forth will includeepoxy resinssuch as the condensation product of epichlorohydrin with bisphenol-A.The epoxy resins in an uncured state will usually be thermoplastic andmay range from low viscosity liquids to high melting point brittlesolids. These resins may be cured by mixing the acid or anhydride withsaid resin and thereafter curing the mixture by treatment at an elevatedtemperature for a predetermined period of time. The resultant productwill have the physical characteristics thereof altered to theirdesirable values as per tains to color stability and flame retardancyand thus be utilized for various purposes such as floor, wall or ceilingsurfacings, as coatings, etc. In addition, some other types of polymericcompounds which may be treated with the acids or anhydrides of the typehereinbefore set forth will include polyphenyl ethers which have beenextended by treatment with styrene, polycarbonates, polyesters,polyurethane foams, etc. The admixing of the novel acid or anhydridewith the aforementioned polymers may be accomplished by any means knownin the art such as, for example, by admixing the com pounds in a mixer,by milling the components, or by extruding the components through asuitable apparatus after admixture thereof, the only criterion beingthat the two components of the mixture are thoroughly admixed in such afashion so that the components are uniformly distributed through thefinished product.

It is also contemplated within the scope of this invention that thenovel flame retardant compositions of matter of the present inventioncomprising a polymeric material and the particular acid or anhydride mayalso contain a sufficient amount of a tinand/or antimonycontainingcompound which will act as a synergist for the flame retardant propertyof said finished composition of matter by enhancing this desirablecharacteristic. Some specific examples of the tin and antimony compoundswhich may be used will include tin compounds in a tetravalent state suchas tin dioxide, tin tetrachloride, methyltin trichloride, ethyltintrichloride, butyltin dichloride, dipropyltin dichloride, trimethyltinchloride, methyltin triacetate, dipropyltin diacetate, diethyltindipropionate, diethyltin dimaleate, dibutyltin dimaleate, dibenzyltindichloride, dimethyltin sulfide, diethyltin sulfide, dimethyltinbis(methylmercaptide), dibutyl tin bis(octhylmercaptide), diethoxytinbis(ethylmercaptide), tin tetrakis(methylmercaptide), diethyltinmercaptoacetate, dioctyltin mercaptoacetate, dilauryltin dithiobutyricacid ethyl ether, diethyl tinS,S'-bis(3,5,5trimethylhexylmercaptoacetate), dibutyltinS,S'-bis(phenoxyethylmercaptoacetate), dibutyltinS,S'-bis(diethyleneglycol laurate mercaptoacetate), antimony trioxide,antimony oxychloride, etc.

Examples of novel flame retardant compositions of matter comprising amixture of a polymeric material and a polyhalo-substitutedpolyhydropolycyclicdicarboxylic acid or anhydride containing adihalosubstituted methylene in a 3 membered ring will include a mixtureof polypropylene and 5,6,7,8,9,9-hexachloro-6,7-dibromomethylene-l,2,3,4,4a,5,8,8aoctahydro-5,8-methano-2,3-naphthalenedicarboxylicacid, polypropylene and 5,6,7,8,9,9-hexachloro-6,7- dibromomethylene-l,2,3 ,4,4a,5,8,8a-octahydro-5,8- methane-2,3-naphthalenedicarboxylicanhydride, polypropylene and 5,6,7,8,9,9-hexachloro-6,7-dichloromethylene-l ,2,3,4,4a,5,8,8a-octahydro-5,8-methano-Z,3-naphthalenedicarboxylic acid, polypropylene and5,6,7,8,9,9-hexachloro-6,7-dichloromethylene-l,2,3,4,4a,5,8,8a-octahydro-5,8-methane-2,3-naphthalenedicarboxylic anhydride; polypropylene andl,4,5,6,7,7-hexachloror-5,6- dichloromethylenebicyclo[2.2.1]heptane-2,3-dicarboxylic acid, polypropylene and l,4,5,6,7,7-hexachloro-5,6-dichloromethylenebicyclo[2.2.1]- heptane-2,3-dicarboxylicanhydride, polyethylene and5,6,7,8,9,9-hexachloro-6,7-dibromomethylenel,2,3,4,4a,5,8,8a-octahydro5,8-methano-2,3-naphthalenedicarboxylic acid, polyethylene and 5,6,7,-8,9,9-hexachlro-6,7-dibromomethylenel,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-

naphthalenedicarboxylic anhydride, polyethylene and5,6,7,8,9,9-hexachloro-6,7-dichloromethylenel,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid, polyethylene and 5,6,7,-8,9,9-hexachloro-6,7,-dichloromethylenel,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride, polyethylene andl,4,5,6,7,7-hexachloro-5,6- dichloromethylenebicyclo[2.2. l]-heptane-2,3 dicarboxylic acid, polyethylene and l,4,5,6,7,7-hexachloro-5,6- dichloromethylenebicyclo[2.2,l1heptanc-2,3- dicarboxylicanhydride, ABS and 5,6,7,8.9,9-hexachloro-6,7-dibromomethylcne-l,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylicacid, ABS and 5,6,7,8,9,9-hexachloro-6,7- dibromometh'ylene-l ,2,3,4,4a,5,8,8a-octahydro-5,8- methano-2,3-naphthalenedicarboxylicanhydride, ABS and 5,6,7,8,9,9-hexachloro-6, 7-dichloromethylene-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicacid, ABS and 5,6,7,8,9,9-hexachloro-6,7-dichloromethylene-l,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylicanhydride, ABS and l,4,5,6,7,7-hexachloro-5,6-dichloromethylenebicyclo[2.2.l ]heptane-2,3- dicarboxylic acid, ABS and1,4,5,6,7,7-hexachloro-5,6- dichloromethylenebicyclo[2.2.l ]heptane-2,3- dicarboxylic anhydride, epoxy resin and 5,6,7-8,9,9hexachloro-6,7-dibromomethylene-l,2,3,4,4a,5,8,8aoctahydro-5,8-methano-2,3-naphthalenedicarboxylic acid,epoxy resin and 5,6,7,8,9,9-hexachloro-6,7- dibromomethylene-l ,2,3,4,4a,5,8,8a-octahydro-5,8- methano2,3-naphthalenedicarboxylicanhydride, epoxy resin and 5,6,7,8,9,9-hexachloro-6,7-dichloromethylene-l,2,3,4,4a,5,8,8a-octahydro-5,8-methane-2,3-naphthalenedicarboxylic acid, epoxy resin and5,6,7,8,9-hexachl0ro-6,7-dichloromethylenel,2,3,4,4a,5,8,8a-octahydro5,8-methano-2,3-naphthalenedicarboxylic anhydride, epoxy resin andl,4,5,6,7,7-hexachloro- 5,odichloromethylenebicyclo[ 2.2. l]heptane-2,3- dicarboxylic acid, epoxy resin and 1,4,5,6,7,7-hexachloro-5,6-

dichloromethylenebicyclo[2.2.l ]heptane-2,3- dicarboxylic anhydride,polyphenyl ether and 5,6,7,8,-9,9-hexachloro-6,7-dibromomethylenel,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylic acid,polyphenyl ether and 5,6,7,8,9,9-hexachloro-6,7-dibromomethylene-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicanhydride, polyphenyl ether and5,6,7,8,9,9-hexachloro-6,7-dichloromethylene- 1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylic acid,polyphenyl ether and 5,6,7,8,9,9-hexachloro-6,7-dichloromethylene-1,2,3,4,-4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicanhydride, polyphenyl ether and l,4,5,6,7,7-hexachloro-5,6-dichloromethylenebicyclo[2.2.l ]-heptane-2,3- dicarboxylic acid,polyphenyl ether and l,4,5,6,7,7- hexachloro-5,6-

dichloromethylenebicyclo[2.2.l ]heptane-2,3- dicarboxylic anhydride,polyester and 5,6,7,8,9,9-hexachloro-6,7-dibromomethylene-l,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylicacid, polyester and 5,6,7,8,9,9-hexachloro-6,7-dibromomethylene-l,2,3,4,4a,5,8,8a -octahydro-5,8-

methano-2,3-naphthalenedicarboxy1ic acid, polyester and5,6,7,8,9,9-hexachloro-6,7-dichloromethylene- 1,2,3 ,4,4a,5 ,8,8a-octahydro- ,8-methano- 2,3naphthalenedicarboxylic anhydride,polyester and 1,4,5 ,6,7,7-hexachloro-5 ,6-dichloromethylenebicyclo[2.2.1]heptane-2,3- dicarboxylic acid, polyesterand 1,4,5,6,7,7- hexachloro-5,6-

dichloromethylenebicyclol2.2.l ]heptane-2,3- dicarboxylic anhydride,etc.

The following examples are given to illustrate the novel flame retardantcompositions of matter of the present invention. However, these examplesare not intended to limit the generally broad scope of the presentinvention in strict accordance therewith.

EXAMPLE I In this example 212 grams (0.5 mole) of 5,6,7,8,9,9-hexachloro-1',2,3 ,4,4a,5 ,8 ,8a-octahydro-5 ,8-methano-2,3-naphthalenedicarboxylic anhydride along with 258 grams (0.5 mole) ofphenl(tribromomethyl)mercury and 200 cc. of benzene are placed in a2-liter flask provided with heating, stirring and refluxing means. Themixture is heated to a temperature of 80 C. and maintained in a range'of80-84 C. for a period of 4 hours. At the end of this time, heating isdiscontinued and the reaction mixture is allowed to return to roomtemperature. The reaction mixture is then treated by fractionaldistillation under reduced pressure to remove benzene and bromobenzeneand the bottoms are allowed to stand. The crystals which formed onstanding are washed with isopropyl alcohol, recrystallized and dried,said crystals being the desired product comprising 5,6,-7,8,9,9-hexachloro-6,7-dibromomethylene-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicanhydride.

EXAMPLE [I In this example 185.5grams (0.5 mole) of 1,4,5,6,7,-7-hexachlorobicyclo[2.2.1]-5-heptene-2,3- dicarboxylic anhydride whichis prepared by condensing maleic anhydride withhexachlorocyclopentadiene along with 258 grams (0.5 mole) of'phenyl(tribromomethyl)mercury and 200 cc. of benzene are placed in a2-liter flask provided with heating, stirring and refluxing means. Themixture is heated to a temperature of 82 C. and refluxed thereat for aperiod of 8 hours. At the end of this time, heating is discontinued, theflask and contents thereof are allowed to return to room temperature andthe mixture is recovered. The benzene solvent and bromobenzene areflashed off and the mixture allowed to cool, the crystal precipiatebeing formed upon standing/The crystals, which are recovered and washedand dried, comprising the desired product, namely1,4,5,6,7,7-hexachloro-5,6- dibromomethylenebicyclo[2.2.1]heptane-2,3-

dicarboxylic anhydride.

EXAMPLE III As in Example 1 above, 220 grams (0.5 mole) of5,6,-7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8a-octahydro-5,8-methano-Z,3naphthalenedicarboxylic acid which is prepared by condensing1,3-butadiene with maleic acid and thereafterfurther condensing theresultant cyclohexenedicarboxylic acid with hexachlorocyclopentadiene,213 grams (0.5 mole) of phenyl(dichlorobromomethyl)mercury and 200 cc.of toluene are placed in an appropriate apparatus similar to thatdescribed in the, above examples. The flask is then heated to atemperature of about 112 C. and refluxed at a temperature in the rangeof from 112-115 C. for a period of 8 hours. Upon completion of thedesired resi- EXAMPLE IV To a round-bottom 2-liter flask provided withheating, stirring and refluxing means is added 198 grams (0.5 mole) of1,4,5,6,7,7-hexachlorobicyclo[2.2.1]-5- heptene-2,3 dicarboxylic acid,213 grams (0.05 mole) of phenyl(dichlorobromomethyl)mercury and 200 cc.of toluene. As in Example 111 above, the mixture is heated to atemperature of 112 C. and refluxed in a range of from 112-l 15 C. for aperiod of 8 hours. Upon completion of the desired residence time, thereaction mixture is allowed to cool to room temperature and the toluenesolvent is removed by flashing and the crystals which form upon standingarewashed, dried and recovered. These crystals comprise the desiredproduct, namely, 1,4,5,6,7,7-hexachloro-5,6-dichloromethylenebicyclo[2.2. l ]heptane-2,3- dicarboxylic acid.

EXAMPLE V In this example 172 grams (0.5 mole) of 5,6,7,8- tetrachloro-l,2,3 ,4,4a,5 ,8,8a-octahydro-5 ,8-methano- 2,3-naphthalenedicarboxylicanhydride, 258 grams (0.5 mole) of phenyl(tribromomethyl)mercury and 200cc. of benzene are placed in a flask provided with heating, stirring andrefluxing means. The mixture is heated to a temperature of C. andrefluxed at a temperature in the range of 80-84 C. for a period of 8hours, at the end of which time heating is discontinued and the mixtureallowed to return to room temperature. The reaction mixture is thentreated by flashing off the benzene solvent and allowing the crystals tocrystallize out upon standing and cooling. The crystals are washed,recrystallized and recovered, said crystals comprising5,6,7,8-tetrachloro-6,7-dibromomethylene-5,8-methano-2,3-naphthalenedicarboxylic anhydride.

EXAMPLE VI To illustrate the efficiency of the aforementioned acids oranhydrides to act as flame retardant additives to polymeric compounds, acommercial high molecular weight polypropylene and5,6,7,8,9,9-hexachloro-6,7- dibromomethylene- 1 ,2,3 ,4,4a,5 ,8,8a-octahydro-5 ,8- methano-2,3-naphthalenedicarboxylic anhydride areadmixed in such proportions that the finished novel composition ofmatter will contain 15 percent by weight of the polyhalosubstitutedanhydride. The mixture is milled for a period of 5- minutes at atemperature of C. and thereafter cut into strips which contain a glasscloth in the center of the strips to prevent dripping. In addition tothe two compounds the polypropylene strip will contain 0.15 grams of acommercial antioxidant comprising a polyhydropolycyclic butane oxidationinhibitor. In addition to this strip of treated polypropylene, anotherstrip of polypropylene which contains only the commercial antioxidant inlike amount is prepared, said polypropylene strip also being providedwith a glass cloth in the center of the strip to prevent dripping. Thetwo strips are burned in a combustion apparatus similar to thatdescribed by C. P. Fennimore and J. F. Martin in the November, 1966issue of Modern Plastics. The strip of polypropylene which contains onlythe oxidation inhibitor will be found to possess an oxygen index (thelowest mole fraction of oxygen sufficient to maintain combustion) ofn=0.180. In contradistinction to this, the strip of polypropylene whichcontains the 5,6,7,8,9,9-hexachloro-6,7-dibromomethylene-l,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride will be found to have anoxygen index much greater than that of the untreated polypropylene aswell as possessing a slower rate of burning.

EXAMPLE VII Another novel composition of matter of the present inventionis prepared by admixing a liquid epoxy resin having an epoxideequivalent weight of I90 and known in the trade as Epon 828 withl,4,5,6,7,7-hexachloro- ,6'-dibromomethylenebicyclo[2.2. I ]heptane-2,3-dicarboxylic anhydride and heating the mixture until it becomeshomogeneous. The homogeneous mixture is then poured into molds which areprepared from glass sheets using Teflon spacers. In addition, a moldrelease agent is also used to facilitate removal of the cured resinsfrom the mold. In addition, the liquid epoxy resin which is not treatedby the addition of the anhydride but contains the mold release agent isalso poured into a second mold similar in nature to the first. The twomolds are placed in an air circulating oven and allowed to cure for aperiod of 6 hours at a temperature of 1 10 C. The sheets are thenremoved from the mold, cut into strips and are evaluated for flameretardancy. The epoxy resin strip which contains the 1,4,5,6,7,7-hexachloro-5,6- dibromomethylenebicyclo[2.2. l ]heptane-2,3-dicarboxylic anhydride will be found to possess a greater flameretardancy, and will also possess excellent heat distortion, temperatureand hardness, as measured by a Shore durometer as contrasted to theepoxy resin which does not contain any flame retardant additlve.

EXAMPLE VIII A novel flame retardant composition of matter of thepresent invention is prepared by admixing 5,6,7,8,9,9-hexachloro-6,7-dichloromethylene-l,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylic acidwith a commercial acrylonitrile-butadiene-styrene (ABS) copolymer insuch a proportion so that the finished composition of matter willcontain percent by weight of the acid. The resulting mixture aftermilling of elevated temperatures is cut into strips similar to thepolypropylene strips of Example VI. In addition, a strip of commercialABS polymer which does not contain the added acid is also prepared. Thetwo strips are then subjected to a flammability test similar in natureto that described in Example VI above. The results of the test will showthat the novel composition of matter of the present invention, namely,5,6,7,8,9,9-hexachloro-6,7-dichloromethylene-l,2,3,4,4a,5,8,8a-octahydro-5,8-methano-Z,3-naphthalenedicarboxylic acid and ABS will possess an oxygenindex greater than the strip of ABS which does not contain the acid andin addition will also possess a rate of burning as measured in secondsper inch much slower than that of the untreated ABS polymer strip.

EXAMPLE IX In like manner a mixture is made by admixing a polymercomprising polyphenylene ether which has been modified by styrene withl,4,5,6,7,7-hexachloro-5.6- dichloromethylenebicyclo[2.2. l]heptane-2,3- dicarboxylic acid at an elevated temperature in order toinsure that the mixture is homogeneous, the final compound containing 20percent by weight of the acid. The mixture is then poured into molds andallowed to cool following which the composition of matter is re coveredand cut into strips. These strips are compared with the other stripswhich contain only the polyphenylene ether (polyphenylene oxide) whichis modified by styrene. A comparison of the oxygen index in aflammability test similar to that set forth in Example VI above willshow that the oxygen index of the novel composition of matter is raisedand the burning rate in air as measured by seconds per inch will belonger than that possessed by the strip of polyphenylene either whichhas been modified with styrene, but which does not contain thel,4,5,6,7,7-hexachloro-5,6 dichloromethylenebicyclo[2.2. l ]heptane-2,3-dicarboxylic acid.

EXAMPLE X A novel flame retardant composition of matteris prepared byadmixing grams of a commercial high molecular weight polypropylene with20 grams of 5,6,7,8- tetrachloro-6,7-dibromomethylene-l,2,3,4,4a,5,8,8aoctahydro-S,8-methano-2,3-naphthalenedicarboxylic anhydride and 0.15grams of a commercial antioxidant comprising a polyhydropolycyclicbutane oxidation inhibitor. The mixture is milled for a period of 5minutes at C. and thereafter cut into strips. In like manner a secondstrip comprising the commercial high molecular weight polypropylene andthe antioxidant is also admixed, milled and cut. The strips are thenburned in a combustion apparatus similar to that described in Example VIabove. The results of this test will show that the composition of mattercomprising the polypropylene and5,6,7,8-tetrachloro-6,7-dibromomethylene-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3- naphthalenedicarboxylicanhydride will have a greater oxygen index and a slower rate or burningthan the strip which contains only the polypropylene and the oxidationinhibitor.

I claim as my invention:

1. A flame retardant composition of matter comprising a polymericmaterial and a polyhalo-substituted polyhydropolycyclicdicarboxylic acidor anhydride thereof having the formula:

in which Y is chlorine or bromine, X is hydrogen or halogen, at leasttwo Xs being halogen, and n is or 1.

2. The flame retardant comprises of claim 1 in which X is chlorine.

3. The flame retardant composition of claim 1 in which X is bromine.

4. The flame retardant composition of claim 1 in which said polymericmaterial is polypropylene and said anhydride is5,6,7,8,9,9-hexachloro-6,7-dibromomethylene-l,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride.

5. The flame retardant composition of claim l in which said polymermaterial is epoxy resin and said anhydride isdibromomethylenebicyclo[2.2. l ]heptane-2,3- dicarboxy-lic anhydride.

6. The flame retardant composition of claim 1 inl,4,5,6,7,7-hexachloro-5,6-'

methano-2,3-naphthalenedicarboxylic anhydridev

1. A FLAME RETARDANT COMPOSITION OF MATTER COMPRISING A POLYMERICMATERIAL AND A POLYHALO-SUBSTITUTED POLYHYDROPOLYCYCLOCDICARBOXYLIC ACIDOR ANHYDRIDE THEREOF HAVING THE FORMULA:
 2. The flame retardantcomprises of claim 1 in which X is chlorine.
 3. The flame retardantcomposition of claim 1 in which X is bromine.
 4. The flame retardantcomposition of claim 1 in which said polymeric material is polypropyleneand said anhydride is 5,6,7,8,9,9-hexachloro-6,7-dibromomethylene-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride.
 5. The flame retardantcomposition of claim 1 in which said polymer material is epoxy resin andsaid anhydride is 1,4,5,6,7,7-hexachloro-5,6-dibromomethylenebicyclo(2.2.1)heptane-2,3-dicarboxylicanhydride.
 6. The flame retardant composition of claim 1 in which saidpolymeric material is an acrylonitrile-butadiene-styrene copolymer andsaid acid is5,6,7,8,9,9-hexachloro-6,7-dichloromethylene-1,2,3,4,4a,-5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic acid.
 7. The flame retardantcomposition of claim 1 in which said polymeric material is polyphenyleneether and said acid is 1,4,5,6,7,7-hexachloro-5,6-dichloromethylenebicyclo(2.2.1)heptane-2,3-dicarboxylicacid.
 8. The flame retardant composition of claim 1 in which saidpolymeric material is polypropylene and said anhydride is 5,6,7,8-tetrachloro-6,7-dibromomethylene-1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride.